Nonaqueous electrolyte secondary battery positive electrode active material and method for producing same, and nonaqueous electrolyte secondary battery which uses positive electrode active material

ABSTRACT

The present invention provides a composite oxide that can achieve a high low-temperature output characteristic, a method for manufacturing the same, and a positive electrode active material in which the generation of soluble lithium is suppressed and a problem of gelation is not caused during the paste preparation. A positive electrode active material for non-aqueous electrolyte secondary batteries, including a lithium-metal composite oxide powder including a secondary particle configured by aggregating primary particles containing lithium, nickel, manganese, and cobalt, or a lithium-metal composite oxide powder including both the primary particles and the secondary particle. The secondary particle has a porous structure inside as a main inside structure, the slurry pH is 11.5 or less, the soluble lithium content rate is 0.5[% by mass] or less, the specific surface area is 3.0 to 4.0 [m 2 /g], and the porosity is more than 50 to 80[%].

CROSS REFERENCE TO RELATED APPLICATIONS

This application is related to two co-pending applications: “NONAQUEOUSELECTROLYTE SECONDARY BATTERY POSITIVE ELECTRODE ACTIVE MATERIAL, METHODFOR PRODUCING SAME, AND NONAQUEOUS ELECTROLYTE SECONDARY BATTERY WHICHUSES POSITIVE ELECTRODE ACTIVE MATERIAL” filed even date herewith in thenames of Hiroko OSHITA, Kazuomi RYOSHI, Taira AIDA, Koji YAMAJI and JiroOKADA as a national phase entry of PCT/JP2018/028589 filed Jul. 31, 2018and “NONAQUEOUS ELECTROLYTE SECONDARY BATTERY POSITIVE ELECTRODE ACTIVEMATERIAL AND METHOD FOR PRODUCING SAME, AND NONAQUEOUS ELECTROLYTESECONDARY BATTERY WHICH USES POSITIVE ELECTRODE ACTIVE MATERIAL” filedeven date herewith in the name of Hiroko OSHITA, Kazuomi RYOSHI, TairaAIDA, Koji YAMAJI and Jiro OKADA as a national phase entry ofPCT/JP2018/028590 filed Jul. 31, 2018; which applications are assignedto the assignee of the present application and are incorporated byreference herein.

TECHNICAL FIELD

The present invention relates to a positive electrode active materialfor non-aqueous electrolyte secondary batteries, a method formanufacturing the positive electrode active material, and non-aqueouselectrolyte secondary batteries in which the positive electrode activematerial is used.

BACKGROUND ART

With the recent spread of portable electronic devices such assmartphones, tablet terminals, and laptop computers, it has beenincreasingly needed to develop high output secondary batteries such assmall and light non-aqueous electrolyte secondary batteries having highenergy density and batteries for hybrid vehicles and electric cars.

Examples of the secondary battery that can meet these needs include alithium ion secondary battery. A lithium ion secondary battery iscomposed of a positive electrode, a negative electrode, an electrolytesolution, and the like, and the active materials of the positiveelectrode and the negative electrode include a material in which lithiumextraction/insertion is possible. Lithium ion secondary batteries arestill being actively researched and developed. Among them, lithium ionsecondary batteries including a layered or spinel lithium-metalcomposite oxide used in the positive electrode material are being put topractical use as batteries having a high energy density since a highvoltage of approximately 4 V can be obtained.

Examples of the positive electrode materials that have been mainlyproposed include a lithium-cobalt composite oxide (LiCoO₂) that isrelatively easily synthesized, a lithium-nickel composite oxide usingnickel that is more inexpensive than cobalt (LiNiO₂), alithium-nickel-manganese-cobalt composite oxide(LiNi_(1/3)Mn_(1/3)Co_(1/3)O₂), and a lithium-manganese composite oxide(LiMn₂O₄) using manganese.

Among them, the lithium-nickel-manganese-cobalt composite oxide has beenattracting attention as a material capable of obtaining a good cyclecharacteristic of a battery capacity, low resistance, and high output,and has been recently considered important for an in-vehicle powersupply, since the composite oxide is also suitable for a power supplyfor electric cars and hybrid vehicles that have limited space formounting.

As a technique for realizing a further high output with such a positiveelectrode material, for example, Patent Literature 1 proposes atechnique in which fine particles containing tungsten and lithium areformed on the surface of primary particles included in a lithium-metalcomposite oxide to reduce the positive electrode resistance and toimprove the output characteristic of a battery. However, tungsten has ahigh scarcity value and belongs to the rare metal, so that the cost ofthe positive electrode active material containing tungsten tends toincrease.

Patent Literature 2 proposes water washing of a lithium-metal compositeoxide. Since excessive lithium unreacted with the metal compositehydroxide is washed away, the initial discharge capacity and the thermalstability are improved. However, there is a defect that the surface ofthe lithium-metal composite oxide is damaged by the water washing andthe required lithium is eluted to deteriorate the output characteristic.

Patent Literature 3 proposes a positive electrode active material fornon-aqueous electrolyte secondary batteries, the positive electrodeactive material including particles having an average particle size of0.05 to 1.0 [μm], containing a positive electrode active material havinga tap density (TD) of 0.8 to 3.0 [g/cm³], and containing 5 to 20 partsby weight of a conductive agent, 0.5 to 10 parts by weight of a binder,and 10 to 120 parts by weight of a solvent, based on 100 parts by weightof the positive electrode active material powder. By using such fineparticles as the positive electrode active material powder, it ispossible to increase the specific surface area corresponding to thereaction area with the electrolyte solution and to improve the outputcharacteristic. However, it is necessary to add a large amount of aconductive assistant in proportion to the specific surface area tosecure the conductivity, and the energy density is accordingly reduced,so that it is required to develop a technique for solving the problem.

Additionally, Patent Literature 4 proposes, as a technique forincreasing the specific surface area and improving the outputcharacteristic, a positive electrode active material having a surfacewith a porous structure and a specific surface area of 1,800 to 2,500[m²/g], and being subjected to a thermal treatment at a temperature of700[° C.] or less.

However, when the thermal treatment temperature is low, the reactivitybetween the lithium source and the metal hydroxide is also decreased,the unreacted excessive lithium is increased, and the crystallinity ofthe positive electrode active material is deteriorated, so that therequired lithium is easily eluted from the positive electrode activematerial itself. As a result, there is concern that dissolution oflithium in the solvent may cause gelation during the paste preparationof the positive electrode active material and the yield is reduced. Thecause of the gelation is largely related to the increase in the pH, thesalt concentration, and the viscosity due to the dissolution of lithiumin the solvent, and thought to be that these factors cause thedeterioration of the binding agent (binder) such as polyvinylidenefluoride (PVDF).

In conventional techniques as described above, there is still a problemto be solved, in order to satisfy the high output characteristicrequired in a positive electrode active material for non-aqueouselectrolyte secondary batteries, and to suppress the gelation during thepaste preparation of the positive electrode active material.

CITATION LIST Patent Literature

Patent Literature 1: JP 2013-125732 A

Patent Literature 2: JP 2007-273106 A

Patent Literature 3: JP 2011-070994 A

Patent Literature 4: JP 2012-248826 A

SUMMARY OF INVENTION Technical Problem

The present invention provides a “lithium-metal composite oxide” used ina “positive electrode active material” and a method for manufacturingthe lithium-metal composite oxide. In the lithium-metal composite oxide,the reactivity between the lithium raw material and the metal compositehydroxide is improved so that a lithium ion secondary batteryincorporating the positive electrode active material can achieve a highoutput characteristic at a low temperature without a water washingtreatment. (Note that the “lithium-metal composite oxide” is used as the“positive electrode active material”. Here, the term “positive electrodeactive material” has a broader meaning, and the term “lithium-metalcomposite oxide” has a narrower meaning.) Furthermore, the presentinvention provides a high-performance positive electrode active materialthat does not cause a problem of gelation during the paste preparationbecause of suppressing the generation of soluble lithium that is easilyeluted from the positive electrode active material itself owing to theincrease of unreacted excessive lithium and lithium that is easilyeluted due to the deterioration of the crystallinity of the positiveelectrode active material and the like.

Solution to Problem

In order to solve the above-mentioned problem, the present inventorshave intensively studied the powder characteristic of a lithium-metalcomposite oxide used as a positive electrode active material fornon-aqueous electrolyte secondary batteries, and the influence of thelithium-metal composite oxide on the charge and discharge characteristicof a battery incorporating the lithium-metal composite oxide. As aresult, the present inventors have found a technique of pulverizing alithium compound powder as a lithium raw material to an optimum particlesize before the mixing and the firing in the manufacturing process of alithium-metal composite oxide. The present inventors have found that byusing the pulverized fine powder lithium compound, a positive electrodeactive material is obtained that does not undergo abnormal particlegrowth while retaining the reactivity with a metal composite hydroxidepowder when firing, and completed the present invention. The presentinvention provides such an excellent positive electrode active materialthat a lithium ion secondary battery incorporating the positiveelectrode active material can achieve a high output characteristic at alow temperature without performing the water washing treatment, thegeneration of soluble lithium is suppressed, and gelation is not causedduring the paste preparation.

A first invention of the present invention based on the findingsdescribed above is a positive electrode active material for non-aqueouselectrolyte secondary batteries, the positive electrode active materialincluding a lithium-metal composite oxide powder including a secondaryparticle configured by aggregating primary particles containing lithium,nickel, manganese, and cobalt, or a lithium-metal composite oxide powderincluding both the primary particles and the secondary particle, whereinthe secondary particle has a porous structure inside as a main insidestructure, a mixed slurry being a mixture of water and the lithium-metalcomposite oxide powder as a slurry solid body component has a pH of 11.5or less at a time when the mixed slurry contains the lithium-metalcomposite oxide at a slurry concentration of 50 [g/L], the lithium-metalcomposite oxide powder contains soluble lithium at a content rate of0.5[% by mass] or less, the lithium-metal composite oxide powder has aspecific surface area of 3.0 to 4.0 [m²/g], and the secondary particlehas a porosity of more than 50 to 80[%].

A second invention of the present invention is a positive electrodeactive material for non-aqueous electrolyte secondary batteries, inwhich the lithium-metal composite oxide powder described in the firstinvention is represented by a general formula:Li_(a)(Ni_(1-w-x)Mn_(w)Co_(x))_(1-y)M_(y)O₂: (0.98≤a≤1.20, 0.01≤w≤0.50,0.01≤x≤0.50, 0.01≤y≤0.10, where M is one or more of Mg, Al, Ti, Fe, Cu,Si, Zn, Mo).

A third invention of the present invention is a positive electrodeactive material for non-aqueous electrolyte secondary batteries, whereinthe lithium-metal composite oxide powder described in the first or thesecond invention has a particle strength of 100 to 160 MPa.

A fourth invention of the present invention is a non-aqueous electrolytesecondary battery including a positive electrode including the positiveelectrode active material for non-aqueous electrolyte secondarybatteries described in the first to the third inventions, whereinΔV_(−20[° C.]) determined by a current rest method is 0.50 [V] or lessat −20[° C.].

A fifth invention of the present invention is a positive electrodemixture paste for non-aqueous electrolyte secondary batteries, thepositive electrode mixture paste including: a solid component; and asolvent, wherein the solid component contains the positive electrodeactive material described in the first to the third inventions, and thepositive electrode mixture paste has a viscosity of 5,000 [mPa·s] orless at 20[° C.] at a time when the positive electrode mixture pasteincludes the solid component and the solvent at a ratio of the solidcomponent [g]/the solvent [g]=1.875.

A sixth invention of the present invention is a method for manufacturinga positive electrode active material for non-aqueous electrolytesecondary batteries, the method including:

a filtration and washing process (A) of washing a metal compositehydroxide with water, or with an alkali and then with water, andcollecting a residual material of the metal composite hydroxide by asolid-liquid separation;

a drying process (B) of obtaining a dried material of the metalcomposite hydroxide by drying the residual material;

a mixing process (C) of forming a mixture of the dried material and afine powder lithium compound having a maximum particle size of 10 [μm]or less; and

a firing process (D) of forming a positive electrode active material fornon-aqueous electrolyte secondary batteries, the positive electrodeactive material including a lithium-metal composite oxide as a firedbody by firing the mixture, in which a lithium-metal composite oxidepowder is manufactured with the metal composite hydroxide containingnickel, manganese, and cobalt and the fine powder lithium compoundhaving a maximum particle size of 10 [μm] or less as raw materials usinga manufacturing process including the processes (A) to (D) in orderdescribed above, the lithium-metal composite oxide powder includes asecondary particle configured by aggregating primary particlescontaining lithium, nickel, manganese, and cobalt or includes both theprimary particles and the secondary particle, the secondary particle hasa porous structure inside as a main inside structure, a slurry has a pHof 11.5 or less at a time when a slurry concentration is 50 [g/L], thelithium-metal composite oxide powder contains 0.5[% by mass] of solublelithium, and the lithium-metal composite oxide powder has a specificsurface area of 3.0 to 4.0 [m²/g].

A seventh invention of the present invention is a method formanufacturing a positive electrode active material for non-aqueouselectrolyte secondary batteries, wherein the metal composite hydroxidedescribed in the sixth invention is produced by a preparing process (a)described below, and the metal composite hydroxide has a coarse densityof more than 50 to 80[%]:

a preparing process (a) for producing a metal composite hydroxide, thepreparing process of stirring water having a water surface in anoxidizing atmosphere and having a maintained temperature of 40 to 60[°C.]; forming a reaction solution by adding a nickel-manganese-cobaltmixed solution, ammonia water, and an alkaline solution to the waterwhile the water is stirred; performing a crystallization treatment in astate where the reaction solution has a maintained pH of 11.0 to 12.5;repeating a crystallization treatment in the reaction solution having aliquid surface in an inert atmosphere or in a non-oxidizing atmospherehaving an oxygen concentration of 0.2[% by volume] or less, and acrystallization treatment in the reaction solution having a liquidsurface in an oxidizing atmosphere having an oxygen concentration ofmore than 21 [% by volume]; and crystallizing a metal compositehydroxide having a controlled coarse density of more than 50 to 80[%].

An eighth invention of the present invention is a method formanufacturing a positive electrode active material for non-aqueouselectrolyte secondary batteries, in which a lithium raw material of thefine powder lithium compound described in the sixth or the seventhinvention, the lithium raw material before pulverized is a lithiumcompound powder having a maximum particle size of 100 [μm] or more andan average particle size of 50 [μm] or more.

A ninth invention of the present invention is a method for manufacturinga positive electrode active material for non-aqueous electrolytesecondary batteries, in which the fine powder lithium compound describedin the sixth to the eighth inventions has a maximum particle size of 10[μm] or less and an average particle size of 5.0 [μm] or less, and thefine powder lithium compound is formed using a pulverizing process (p)described below:

a pulverizing process (p) of producing a fine powder lithium compoundhaving a maximum particle size of 10 [μm] or less and an averageparticle size of 5.0 [μm] or less by pulverizing a lithium compoundpowder being a lithium raw material having a maximum particle size of100 [μm] or more and an average particle size of 50 [μm] or more.

A tenth invention of the present invention is a method for manufacturinga positive electrode active material for non-aqueous electrolytesecondary batteries, in which the lithium raw material described in theeighth or the ninth invention is lithium carbonate, lithium hydroxide,or a mixture of the lithium carbonate and the lithium hydroxide.

An eleventh invention of the present invention is a method formanufacturing a positive electrode active material for non-aqueouselectrolyte secondary batteries, in which the lithium-metal compositeoxide powder described in the sixth to the tenth inventions isrepresented by a general formula:Li_(a)(Ni_(1-w-x)Mn_(w)Co_(x))_(1-y)M_(y)O₂: (0.98≤a≤1.20, 0.01≤w≤0.50,0.01≤x≤0.50, 0.01≤y≤0.10, where M is one or more of Mg, Al, Ti, Fe, Cu,Si, Zn, Mo).

A twelfth invention of the present invention is a method for evaluatinga characteristic of a positive electrode active material for non-aqueouselectrolyte secondary batteries, the characteristic being a “slurry pH”indicating a pH of a slurry containing water and the positive electrodeactive material as a solid body component, the method including: addingthe positive electrode active material to the water so that the slurrycontains the positive electrode active material at a concentration of 50[g/L]; maintaining a state where the slurry is stirred for 30 minutes;and obtaining the slurry pH by measuring the pH of the slurry with a “pHmeter” in the state where the slurry is stirred.

A thirteenth invention of the present invention is a method forevaluating a characteristic of a positive electrode active material fornon-aqueous electrolyte secondary batteries, the positive electrodeactive material for non-aqueous electrolyte secondary batteriescontaining lithium, the characteristic being a “soluble lithium contentrate” indicating a lithium amount contained in the positive electrodeactive material soluble in water being a liquid component of a slurrycontaining the positive electrode active material and the water, themethod including: adding the positive electrode active material to thewater so that the slurry contains the positive electrode active materialat a concentration of 20 [g/L]; maintaining a state where the slurry isstirred for 10 minutes; filtering the slurry; and obtaining the solublelithium content rate by measuring the lithium contained in an obtainedfiltrate with an ICP optical emission spectrometer.

A fourteenth invention of the present invention is a method forevaluating a characteristic of a positive electrode active material fornon-aqueous electrolyte secondary batteries, the characteristic being aporosity representing a measure of an amount of an internal space of thepositive electrode active material, the method including: a firstprocess of embedding a lithium-metal composite oxide in a resin; asecond process of exposing a cross section of a particle of thelithium-metal composite oxide embedded in the resin by cutting theparticle using a cross-section polisher by argon sputtering; a thirdprocess of observing the exposed cross section of the particle using ascanning electron microscope; and a fourth process of determining aporosity by analyzing an image of the observed cross section of theparticle with image analysis software so that a void of the image isanalyzed as a black part and a dense portion is analyzed as a white partand calculating an area ratio of the black part/(the black part+thewhite part) for the cross section of any 20 or more of the particles.

Advantageous Effects of Invention

The present invention provides a positive electrode active material fornon-aqueous electrolyte secondary batteries that is obtained through aprocess of mixing a metal composite hydroxide and a fine powder lithiumcompound produced by pulverizing a lithium compound powder as a lithiumraw material so that the maximum particle size is 10 [μm] or less andthe average particle size is 5.0 [μm] or less, and of firing themixture, the positive electrode active material so excellent that alithium ion secondary battery incorporating the positive electrodeactive material can achieve a high output characteristic at a lowtemperature without water washing, the generation of soluble lithium issuppressed, and gelation is not caused during the paste preparation.Therefore, the industrial significance of the present invention isextremely large.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a process flowchart in a method for manufacturing a positiveelectrode active material according to the present embodiment.

FIG. 2 is a process flowchart in a method for manufacturing a metalcomposite hydroxide according to the present embodiment.

FIG. 3 is a schematic cross sectional view of metal composite hydroxideparticles 11 according to the present embodiment.

FIG. 4 is a view showing an example of a laminate cell prepared forevaluation of a low-temperature output characteristic according toExamples.

FIG. 5 is an example of a cross sectional SEM image showing that theinternal structure of a lithium-metal composite oxide particlesaccording to the present embodiment is a porous structure.

DESCRIPTION OF EMBODIMENTS

One embodiment of the present invention will be described below.

The present embodiment is not limited to the description below, and canbe modified without departing from the scope of the present invention.

FIG. 1 is a process flowchart in a method for manufacturing a positiveelectrode active material according to the present embodiment. Thefollowing description of the method for manufacturing will be made inaccordance with the process flow shown in FIG. 1 .

<Preparing Process (a) of Metal Composite Hydroxide>

FIG. 2 is a process flow chart in the method for producing a metalcomposite hydroxide according to the present embodiment.

First, a nickel-manganese-cobalt mixed solution as a raw materialsolution prepared by mixing of aqueous solutions of nickel, manganese,cobalt, and if necessary a metal compound such as an M element compound(preferably, the aqueous solution prepared using a hydrate), an alkalinesolution that is used for pH adjustment (such as an aqueous sodiumhydroxide solution), and ammonia water that is used for ammoniaconcentration (NH₄ ⁺) adjustment are prepared.

Next, in the manufacturing of the metal composite hydroxide according tothe present embodiment, water (preferably, pure water such asion-exchanged water in which impurities are controlled) was put into areaction tank in an oxidizing atmosphere (that preferably has an oxygenconcentration of more than 21[% by volume] and may be typically theatmosphere) controlled to be in the temperature range of 40 to 60[° C.]by heating, the raw material solution and the ammonia water weresupplied at a constant rate to form a reaction solution while the insideof the reaction tank was stirred with a stirrer so that the liquidtemperature was in the range of 40 to 60[° C.] and while the supplyamount of an alkaline solution was controlled so that the pH of thewater (at a standard liquid temperature of 25[° C.]) was in the range of11.0 to 12.5, and the treatment was performed from the start of thecrystallization in the range of 0.5 hour to produce a metal compositehydroxide. The liquid supply was stopped after the crystallization wascompleted.

Then, the crystallization state is changed by repeating a predeterminednumber of times of changing the atmosphere in the reaction tank from theoxidizing atmosphere to an inert atmosphere or a non-oxidizingatmosphere having a controlled oxygen concentration of 0.2[% by volume]or less, and the coarse density of the obtained metal compositehydroxide is controlled to more than 50 to 80[%], so that anickel-manganese-cobalt composite hydroxide having a porous structure ismanufactured.

The number of repeating times of the crystallization treatment withchanging the atmosphere in the reaction tank is determined by measuringthe coarse density, and the crystallization time in each crystallizationtreatment is appropriately set in the range of 0.5 hour to 4 hours andthe total crystallization time is appropriately set in the range of 0.5to 5 hours depending on the size of the hydroxide, the degree of thedispersion of the voids, the thickness of the outer shell section, andthe like.

As described above, by setting the atmosphere in the reaction tank to anoxidizing atmosphere (the atmosphere), an inert atmosphere, or anon-oxidizing atmosphere in which the oxygen concentration is controlledto 0.2[% by volume] or less, the coarse density of the obtained metalcomposite hydroxide powder is controlled.

Here, when the temperature in the reaction tank is less than 40[° C.],the particle size of the generated metal composite hydroxide is toolarge, and when the temperature is more than 60[° C.], the particle sizeof the metal composite hydroxide is too small. Such a particle size isundesirable because of its influence on a lithium-metal composite oxidemanufactured in the subsequent process. When the pH in the reaction tankat the beginning of forming the reaction solution is less than 11.0, theconcentration of the sulfate remaining in the positive electrode activematerial is high and the output characteristic of a batteryincorporating the positive electrode active material is deteriorated, sothat such a pH is undesirable. When the pH is more than 12.5, theparticle size is too small, so that such a pH is undesirable. Thecrystallization treatment can be stabilized by controlling the ammoniaconcentration (NH₄ ⁺) in the range of 5 to 30 [g/L], preferably in therange of 10 to 20 [g/L].

When the coarse density of the obtained metal composite hydroxide isless than 50[%], the voids in the porous structure are not sufficientlydispersed, and when the coarse density is more than 80[%], the obtainedmetal composite hydroxide cannot maintain the strength as a particlehaving a porous structure and is easily crushed in the subsequentmanufacturing process, so that a desired positive electrode activematerial is not obtained.

The coarse density can be measured by observing the cross sectionalstructure of the obtained metal composite hydroxide particles using ascanning electron microscope (SEM). Specifically, for the evaluation ofthe coarse density, the cross sectional area of the particles and thevoid area inside the particles are determined using image analysissoftware and the coarse density is calculated by a formula of “(voidarea inside particles)/(cross sectional area of particles)×100[%]”.

When applied to the secondary particle according to the presentembodiment, the term “coarse density” means a value that is obtainedfrom the result of the image analysis of the cross section of theobtained metal composite hydroxide particles using a scanning electronmicroscope and image analysis software, and is represented by a formulaof “(void area inside secondary particle/cross sectional area ofsecondary particle)×100[%]”.

For example, in the cross section of composite hydroxide particles 11having a particle size d shown in FIG. 3 , the coarse density is a valuerepresented by “(area of void 14)/(sum of cross sectional area ofprimary particles 12 and area of void 14)×100”. That is, the higher thecoarse density is, the coarser the structure inside a secondary particle13 is, and the lower the coarse density is, the denser the structureinside the secondary particle 13 is.

Specifically, 20 cross sections of the secondary particle 13 having aparticle size of 80[%] or more of the volume average particle diameter(MV) are randomly selected, the coarse densities of the cross sectionsof the secondary particle 13 are measured, and the average value(average coarse density) is calculated.

<Filtration and Washing Process (A)⋅Drying Process (B)>

In a filtration and washing process (A), the reaction solution after thecrystallization treatment is filtered to separate the residual materialof the crystallized metal composite hydroxide from the filtrate. In theprocess, the obtained residual material of the metal composite hydroxideis washed with an alkali using an alkaline solution such as a sodiumhydroxide solution to remove a sulfate ion (SO₄ ²⁻), a chlorine ion(Cl⁻), and the like contained in the metal composite hydroxide, and thenwashed again with pure water such as ion-exchanged water in whichimpurities are controlled to remove impurities such as a sodium ion(Na⁺), so that the metal composite hydroxide being a washed residualmaterial is obtained through the water washing.

Furthermore, the metal composite hydroxide being a washed residualmaterial is put in a dryer and dried at a temperature in the range of100 to 150[° C.] to obtain a dried material of the metal compositehydroxide dry powder.

<Pulverizing Process (p) of Lithium Compound Powder>

This is a process of finely pulverizing a lithium compound powder havinga maximum particle size of 100 [μm] or more as a lithium raw material.The reason for using a lithium compound powder having a maximum particlesize of 100 [μm] or more as a lithium raw material is that such alithium compound powder is pulverized to a powder having many newsurfaces that are not under an influence of surface deterioration due tomoisture absorption and the like, so that a fine powder lithium compoundcan be obtained having an increased contact surface and reactivity withthe metal composite hydroxide. Another reason is that a batteryincorporating the lithium-metal composite oxide manufactured through amixing and firing process as a positive electrode active material has animproved low-temperature output characteristic.

The pulverized fine powder lithium compound preferably has a maximumparticle size of 10.0 [μm] or less, and more preferably 8.0 [μm] orless. Furthermore, the average particle size is preferably 5.0 [μm] orless, and more preferably 3.5 [μm] or less. When the maximum particlesize is more than 10.0 [μm] or the average particle size is more than5.0 [μm], the reactivity is decreased between the fine powder lithiumcompound and the mixed metal composite hydroxide when firing, and thelow-temperature output characteristic is deteriorated of a batteryincorporating the manufactured lithium-metal composite oxide as apositive electrode active material.

In the pulverizing, a general pulverizer can be used. For example, a jetmill or a ball mill can be used, and the pulverization condition is setso that the maximum particle size is 10.0 [μm] or less. After thepulverizing, a powder having a particle size of more than 10.0 [μm] maybe removed by sieving to obtain the fine powder lithium compound havinga predetermined particle size. The lower limit of the particle size isnot particularly limited, and in consideration of the performance of thepulverizer, the average particle size is about 0.1 [μm].

For the confirmation of the maximum particle size and the averageparticle size, a laser diffraction/scattering type particle sizedistribution measuring device can be used. In the measurement with themeasuring device, the particle size is measured by a laserdiffraction/scattering method with a circulating slurry obtained byadding a liquid to a sample to be measured, and the circulating slurryis irradiated with an ultrasonic wave for the deagglomeration of thesecondary particle, so that almost all the particles to be measured areprimary particles.

The lithium compound powder is not particularly limited, and lithiumcompounds can be used such as lithium carbonate (Li₂CO₃: melting point723[° C.]), lithium hydroxide (LiOH: melting point 462[° C.]), lithiumnitrate (LiNO₃: melting point 261[° C.]), lithium chloride (LiCl:melting point 613[° C.]), and lithium sulfate (Li₂SO₄: melting point859[° C.]). Lithium carbonate or lithium hydroxide is particularlypreferably used in consideration of the ease of the handling and thequality stability.

<Mixing Process (C) and Firing Process (D)>

The fine powder lithium compound obtained by pulverizing the lithiumcompound powder as a lithium raw material in the pulverizing process (p)and the dry powder of the metal composite hydroxide obtained through thedrying process (B) are mixed in a mixing process (C).

The fine powder lithium compound and the metal composite hydroxidepowder are mixed so that the ratio of the sum of the numbers of nickel,manganese, and cobalt atoms and the number of lithium atoms is in therange of 1.00 to 1.20 in the lithium-metal composite oxide. When theratio is less than 1.00, lithium atoms are not incorporated into thelithium site, 3a site, so that a battery incorporating the manufacturedlithium-metal composite oxide as a positive electrode active materialcannot achieve the target battery characteristic.

The term “site” refers to a crystallographically equivalent latticeposition. A case where an atom is present at a lattice position isreferred to as a case where “a site is occupied”, and the site is calledan occupied site. For example, LiCoO₂ has three occupied sites that arecalled a lithium site, a cobalt site, and an oxygen site, or also calleda 3a site, a 3b site, and a 6c site. When the ratio is more than 1.20,the sintering is promoted and the particle size and the crystallitediameter are too large, so that the cycle characteristic isdeteriorated.

Next, the mixture of the fine powder lithium compound and the metalcomposite hydroxide powder (hereinafter also referred to as the lithiummixture) is subjected to a firing process (D) of firing at a temperaturein the range of 800 to 950[° C.] in the atmosphere.

When the firing temperature of this firing is less than 800[° C.],satisfactory battery characteristic cannot be obtained because thereactivity is reduced and unreacted excessive lithium is increased inthe obtained lithium-metal composite oxide, or the crystallinity and thelike is deteriorated owing to the insufficiently adjusted crystalstructure and the required lithium is easily eluted from the positiveelectrode active material itself. The tendency is particularlyremarkable when a mixed slurry being a mixture of water and thelithium-metal composite oxide powder fired at 800[° C.] or less as asolid body component contains the lithium-metal composite oxide powderat a concentration of 50 [g/L] and has a pH of more than 11.5.

Furthermore, as described above, the unreacted excessive lithium isincreased and the lithium is easily eluted from the positive electrodeactive material itself owing to the deterioration of the crystallinityof the positive electrode active material, so that a problem of solublelithium is also caused as described below. Meanwhile, when the firingtemperature is more than 950[° C.], there is possibility that sinteringmay occur vigorously between the lithium-metal composite oxide particlesto cause abnormal particle growth.

The lithium mixture may be calcined at 600 to 780[° C.] before thefiring. By the calcination, the reaction in the firing proceeds moregently, so that the unreacted excessive lithium is reduced and thecrystallinity is improved in the obtained lithium-metal composite oxide.The retention time at the calcination temperature is preferably 0.5 to10 hours, and more preferably 2 to 4 hours. The calcination atmospheremay be the atmosphere or an oxidizing atmosphere, and preferably has anoxygen concentration of 18 to 100[% by volume].

It is not always necessary to cool the lithium mixture to roomtemperature between the calcination and the subsequent firing (alsoreferred to as main firing), and the main firing may be performed byraising the temperature from the calcination temperature.

<Deagglomeration and Crushing Process (E)>

In the lithium-metal composite oxide powder obtained in the firingprocess (D), the secondary particles are sometimes aggregated orslightly sintered.

In such a case, the aggregate or the sintered body of the lithium-metalcomposite oxide powder is preferably subjected to deagglomeration andcrushing. As a result, the particle size and the particle sizedistribution of the obtained lithium-metal composite oxide powder can beadjusted to a suitable range as a positive electrode active material.

As such a deagglomeration and crushing method, known means can be used,and for example, a pin mill, a hammer mill, or the like can be used. Inthis case, it is preferable to appropriately adjust the deagglomerationand crushing force to such an extent that the secondary particles arenot destroyed.

The particle size such as the maximum particle size or the averageparticle size and the particle size distribution are required to bemeasured using a laser diffraction/scattering type particle sizedistribution measuring device in the same manner as in the pulverizingprocess (p).

<Positive Electrode Active Material for Non-Aqueous ElectrolyteSecondary Batteries>

The positive electrode active material for non-aqueous electrolytesecondary batteries, according to the present embodiment, is alithium-metal composite oxide powder including a secondary particleconfigured by aggregating primary particles containing lithium, nickel,manganese, and cobalt, or a lithium-metal composite oxide powderincluding both the primary particles and the secondary particle, whereina mixed slurry being a mixture of water and the lithium-metal compositeoxide powder as a solid body component has a pH of 11.5 or less at atime when the mixed slurry contains the lithium-metal composite oxidepowder at a concentration of 50 [g/L], the lithium-metal composite oxidepowder contains soluble lithium at a content rate of 0.5[% by mass] orless, the lithium-metal composite oxide powder has a specific surfacearea of 3.0 to 4.0 [m²/g], and the secondary particle has a porosity ofmore than 50 to 80[%]. The component composition of the lithium-metalcomposite oxide powder is preferably represented by a general formula:Li_(a)(Ni_(1-w-x)Mn_(w)Co_(x))_(1-y)M_(y)O₂: (0.98≤a≤1.20, 0.01≤w≤0.50,0.01≤x≤0.50, 0.01≤y≤0.10 wherein M is one or more of Mg, Al, Ti, Fe, Cu,Si, Zn, and Mo).

Furthermore, in a non-aqueous electrolyte secondary battery including apositive electrode including the positive electrode active material fornon-aqueous electrolyte secondary batteries according to theabove-mentioned embodiment, “ΔV_(−20[° C.]) determined by a current restmethod at −20[° C.]” is 0.50 [V] or less.

<Internal Structure of Lithium-Metal Composite Oxide Powder>

The lithium-metal composite oxide in the present embodiment has a porousstructure inside the secondary particle. The positive electrode activematerial including the lithium-metal composite oxide powder having aporous structure has an excellent output characteristic due to anincrease in the contact area with an electrolyte solution. Furthermore,the lithium-metal composite oxide can maintain the filling property whenused as a positive electrode active material unlike that having a hollowstructure. The lithium-metal composite oxide in the present embodimenthas good particle strength despite having a porous structure.

The term “having a porous structure inside the secondary particle”refers to having a structure in which voids inside the secondaryparticle are dispersed throughout the particle. The porous structure canbe confirmed by observing a cross section of the lithium-metal compositeoxide powder with a scanning electron microscope as shown in FIG. 5 .

The lithium-metal composite oxide powder having a porous structurepreferably has a porosity of 40 to 90[%], and more preferably more than50 to 80[%] as measured by observing the cross section of the particles.As a result, the contact area of the positive electrode active materialwith the electrolyte solution can be sufficient while the particlestrength is maintained within an allowable range without excessivelyreducing the bulk density of the obtained positive electrode activematerial.

In the present embodiment, the secondary particle has a porous structureand is not limited to such a particle. It is possible to mix secondaryparticles having a porous structure, a solid structure, and a hollowstructure in combination. For example, at the time of mixing and firinga metal hydroxide serving as a source of a transition metal such asnickel, manganese, or cobalt, it is also possible to mix a metalhydroxide having a solid structure, a hollow structure, or a porousstructure in combination or at a ratio by adjusting the crystallizationcondition in the manufacturing process and the like, and thelithium-metal composite oxide obtained in such a manner has an advantagein the overall composition and the particle size stabler than those of alithium-metal composite oxide prepared by simply mixing a solid product,a hollow product, and a porous product.

<Method for Evaluating Positive Electrode Active Material>

[Slurry pH]

The term “slurry pH” refers to the pH of a mixed slurry being a mixtureof water and the lithium-metal composite oxide powder as a solid bodycomponent at a time when the mixed slurry contains the lithium-metalcomposite oxide powder at a concentration of 50 [g/L]. To thelithium-metal composite oxide, water (preferably, water such asion-exchanged water in which impurities are controlled) is added so thatthe mixed slurry has the above-mentioned concentration, the mixed slurryis maintained to be stirred for 30 minutes, and the pH of the preparedslurry is measured with a pH meter in the state where the slurry isstirred. Here, when the stirring time is more than 30 minutes, carbondioxide in the atmosphere is actively absorbed from the slurry liquidsurface and the pH easily fluctuates, so that such a stirring time isundesirable.

For calibrating the pH meter, three types of standard buffer solutionssold by reagent manufacturers for pH calibration of pH4, pH7, and pH9are used. For confirmation of the calibration, a standard buffersolution for pH calibration of pH 10 is used as a check sample.

By confirming the slurry pH, the overall quality of the reactivitybetween the fine powder lithium compound and the metal hydroxideparticles can be known.

The upper limit of the slurry pH is preferably 11.5 or less, morepreferably 11.3 or less, and particularly preferably 11.1 or less. Thelower limit of the slurry pH is preferably 10.5 or more, more preferably10.7 or more, and particularly preferably 10.9 or more.

When the slurry pH is more than 11.5, it is considered that unreactedexcessive lithium is increased owing to the insufficient mixing in themixing process (C) and the reduced reactivity in the firing process (D),and when the slurry pH is less than 10.5, it is considered that in themixing process (C), the supply amount of the fine powder lithiumcompound is insufficient with respect to the supply amount of the metalhydroxide powder.

[Soluble Lithium]

To the lithium-metal composite oxide, water (preferably, pure water suchas ion-exchanged water in which impurities are controlled) is added sothat the mixture contains the lithium-metal composite oxide at aconcentration of 20 [g/L], the mixture is stirred for 10 minutes andthen filtered, and the lithium contained in the filtrate is measured byan ICP optical emission spectrometer. Here, the elemental analyzer usedfor the measurement is not particularly limited as long as lithium isdirectly measured with the analyzer. Examples other than the ICP opticalemission spectrometer include an atomic absorption spectrometer, aflameless atomic absorption spectrometer, a microwave plasma atomicemission spectrometer, and an ion chromatograph.

As a method for evaluating excessive lithium, a neutralization titrationmethod is generally used. In the method, excessive lithium has a form oflithium hydroxide (LiOH) or lithium carbonate (Li₂CO₃). That is,hydroxide ions (OH⁻) and carbonate ions (CO₃ ²⁻) that are anionscorresponding to lithium ions (Li⁺) are titrated with a hydrochloricacid standard solution to indirectly analyze the lithium.

In general, on the surface (or the crystal grain boundary) of thelithium-metal composite oxide after firing, excessive lithium remains inthe form of lithium hydroxide (LiOH), lithium carbonate (Li₂CO₃),lithium sulfate (Li₂SO₄), and the like, and these excessive lithiumcompounds are eluted by water washing. When the reaction between thelithium compound and the metal composite hydroxide is insufficient orwhen excessive washing is performed, the lithium is easily eluted fromthe crystal lattice.

Therefore, the neutralization titration method cannot be applied to thedetection of lithium having another form such as lithium eluted from thepositive electrode active material itself owing to the deterioration ofthe crystallinity of the positive electrode active material that is thelithium-metal composite oxide.

Therefore, in order to accurately evaluate soluble lithium that is thetotal lithium amount dissolved in water, electrolyte solution, and thelike, as well as the excessive lithium compound remaining on the surfaceof the positive electrode active material, it is necessary to use theelemental analyzer with which lithium can be directly measured.Furthermore, since there is no need to separate and quantify lithiumhydroxide (LiOH) and lithium carbonate (Li₂CO₃) in the evaluation of thesoluble lithium, it is necessary to avoid applying the neutralizationtitration method that is an indirect analysis method in order to improvethe accuracy and the precision of the analysis.

The soluble lithium content measured by the above-mentioned method forevaluating is represented by a formula of “{(measured value by elementalanalyzer [g/L])×(slurry volume [L])/(slurry solid body component[g])}×100[% by mass]”, and is preferably 0.5[% by mass] or less, morepreferably 0.4[% by mass] or less, and particularly preferably 0.3[% bymass] or less. It is particularly preferable that lithium should not bedetected, so that the lower limit of analysis (quantitation) of thesoluble lithium content is about 0.0005[% by mass] when the conditionfor preparing the filtrate and the detection limit of the elementalanalyzer are considered.

If the slurry pH is less than 10.5 while the soluble lithium content isless than the analysis lower limit of 0.0005[% by mass], it isconsidered that the addition amount of the fine powder lithium compoundis insufficient with respect to the addition amount of the metalhydroxide powder in the mixing process (C).

[Specific Surface Area]

The specific surface area can be evaluated with the BET specific surfacearea determined by the nitrogen gas adsorption method based on the BETequation.

The specific surface area of the lithium-metal composite oxide ispreferably 3.0 to 4.0 [m²/g]. When the specific surface area is lessthan 3.0 [m²/g], a sufficient reaction area with lithium cannot beensured. When the specific surface area is more than 4.0 [m²/g], thefilling property is deteriorated.

As described above, it is necessary that the “slurry pH”, the “solublelithium”, and the “specific surface area” are within the preferredranges in order to obtain a high-performance positive electrode activematerial that does not cause a problem of gelation during thepreparation of the positive electrode mixture paste using the positiveelectrode active material including the obtained metal composite oxidepowder.

[Porosity]

The porosity can be measured by observing an arbitrary cross section ofthe lithium-metal composite oxide particles with a scanning electronmicroscope, and performing image analysis.

At that time, the evaluation is performed by the following method forevaluating the porosity.

—Method for Evaluating Porosity—

The porosity can be determined by performing the following processes inorder: a first process of embedding a lithium-metal composite oxide in aresin; a second process of exposing a cross section of a particle of thelithium-metal composite oxide embedded in the resin by cutting theparticle using a cross-section polisher by argon sputtering; a thirdprocess of observing the exposed cross section of the particle using ascanning electron microscope; and a fourth process of determining aporosity by analyzing an image of the observed cross section of theparticle with image analysis software so that a void of the image isanalyzed as a black part and a dense portion is analyzed as a white partand calculating an area ratio of the black part/(the black part+thewhite part) for the cross section of any 20 or more of the particles.

[Particle Strength]

The particle strength is preferably 80 to 250 MPa, more preferably 90 to180 MPa, and particularly preferably 100 to 160 MPa, irrespective of theinternal structure of the lithium-metal composite oxide powder. When theparticle strength is less than 80 MPa, many “cracks” are caused in thelithium-metal composite oxide particles after the charge and discharge,the capacity is sometimes reduced, and the battery is sometimesexpanded. When the particle strength is more than 250 MPa, the fillingproperty is deteriorated and in the production of the positive electrodefilm of the battery, a positive electrode film cannot be sometimesprepared. Furthermore, when a charge and discharge cycle is performedwith a positive electrode film having poor filling property, thecapacity is greatly reduced, and the cycle characteristic is extremelydeteriorated.

The method for evaluating the particle strength is not particularlylimited, and the particle strength can be determined, for example, bymeasuring each particle using a micro compression tester.

<Non-Aqueous Electrolyte Secondary Battery>

[Positive Electrode]

The positive electrode mixture used for forming the positive electrode,and each material included in the positive electrode mixture will bedescribed.

The powdered positive electrode active material according to the presentembodiment, a conductive material, and a binding agent are mixed,activated carbon and a solvent for the purpose of adjusting theviscosity are added if necessary, and the resulting mixture is kneadedto prepare a positive electrode mixture paste. The mixing ratio of eachmaterial in the positive electrode mixture paste is also an importantfactor in determining the performance of the lithium secondary battery.

The mixing ratio of each material in the positive electrode mixturepaste is not particularly limited, and in the same manner as in thepositive electrode of a general lithium secondary battery, the positiveelectrode mixture paste preferably contains 60 to 95[% by mass] of thepositive electrode active material, 1 to 20[% by mass] of the conductivematerial, and 1 to 20[% by mass] of the binding agent based on 100[% bymass] of the total solid components in the positive electrode mixturepaste excluding the solvent.

Furthermore, the viscosity of the positive electrode mixture paste canbe measured using a vibrating viscometer.

In the measurement using the vibrating viscometer, a vibrator in a fluidis resonated at a constant amplitude and frequency to measure theviscosity using the correlation between the vibrating force to move thevibrator and the viscous resistance of the fluid, and it is possible tomeasure viscosity as high as 10,000 [mPa·s].

In the present embodiment, 10 g or more of the positive electrodemixture paste mixed so that the solid component [g]/the solvent[g]=1.875 for confirming the viscosity was put in a predeterminedcontainer, and the fluid temperature was adjusted to 20° C. in a waterbath to measure the viscosity. The calibration of the vibratingviscometer is preferably two-point calibration in which JS-200(viscosity at 20[° C.]: 170 [mPa·s]) and JS-2000 (viscosity at 20[° C.]:1800 [mPa·s]) are used as standard solutions for calibration of aviscometer that are specified in JIS-Z-8809. The above-mentioned ratio“1.875” represents a solid-liquid ratio in the positive electrodemixture paste used for preparing a positive electrode that provides afavorable characteristic to a secondary battery as in a case accordingto the present embodiment.

The obtained positive electrode mixture paste is applied to, forexample, the surface of an aluminum foil current collector, and dried toevaporate the solvent. If necessary, the positive electrode mixturepaste is pressed with a roll press or the like to increase the electrodedensity. A sheet-shaped positive electrode can be prepared in such amanner. The prepared sheet-shaped positive electrode is subjected toprocessing such as cutting into an appropriate size in accordance with atarget battery, and can be used for preparing the battery. The methodfor preparing the positive electrode is not limited to theabove-described example, and may be another method.

Examples of the conductive material used for preparing the positiveelectrode include graphite (natural graphite, artificial graphite,expanded graphite, and the like) and carbon black-based materials suchas acetylene black and Ketjen black.

The binding agent (binder) plays a role of binding the active materialparticles, and examples of the binding agent include polyvinylidenefluoride (PVDF), fluorine-containing resins such aspolytetrafluoroethylene, ethylene propylene diene rubber, and fluorinerubber, and thermoplastic resins such as styrene-butadiene,cellulose-based resins, polyacrylic acid, polypropylene, andpolyethylene. If necessary, a solvent that disperses the positiveelectrode active material, the conductive material, and the activatedcarbon, and dissolves the binding agent is added to the positiveelectrode mixture.

As the solvent, specifically, an organic solvent such asN-methyl-2-pyrrolidone (NMP) can be used.

To the positive electrode mixture, activated carbon can be added inorder to increase the capacity of the electric double layer.

[Negative Electrode]

The used negative electrode is produced in such a way that a bindingagent is mixed and a suitable solvent is added to a negative electrodeactive material that can absorb and desorb metallic lithium, lithiumalloys, and a lithium ion to form a paste-like mixture, the resultingnegative electrode mixture paste is applied to the surface of a metalfoil current collector such as copper, dried, and, if necessary,compressed and formed to increase the electrode density.

Examples of the negative electrode active material include naturalgraphite, artificial graphite, organic compound fired bodies such as aphenol resin, and powdered carbon materials such as coke. In this case,as the negative electrode binding agent, a fluorine-containing resinsuch as polyvinylidene fluoride (PVDF) can be used in the same manner asin the positive electrode, and as the solvent that disperses the activematerial and the binding agent, an organic solvent such asN-methyl-2-pyrrolidone (NMP) can be used.

[Separator]

A separator is interposed between the positive electrode and thenegative electrode. The separator separates the positive electrode andthe negative electrode and retains the electrolyte, and may be a thinfilm of polyethylene, polypropylene, or the like having many fine holes.

[Non-Aqueous Electrolyte Solution]

The non-aqueous electrolyte solution is produced by dissolving a lithiumsalt as a supporting salt in an organic solvent. As the organic solvent,one can be used alone or two or more can be mixed and used selected fromcyclic carbonates such as ethylene carbonate (EC), propylene carbonate(PC), butylene carbonate (BC), and trifluoropropylene carbonate (TFPC),chain carbonates such as diethyl carbonate (DEC), dimethyl carbonate(DMC), ethyl methyl carbonate (EMC), and dipropyl carbonate (DPC), ethercompounds such as tetrahydrofuran (THF), 2-methyltetrahydrofuran(2-MeTHF), and dimethoxyethane (DME), sulfur compounds such as ethylmethyl sulfone and butanesultone, and phosphorus compounds such astriethyl phosphate and trioctyl phosphate.

As the supporting salt, lithium hexafluorophosphate (LiPF₆), lithiumtetrafluoroborate (LiBF₄), lithium perchlorate (LiClO₄), lithiumhexafluoroarsenate (LiAsF₆), lithium bis(trifluoromethanesulfonyl)imide(LiN(CF₃SO₂)₂), or the like, or a composite salt thereof can be used.

Furthermore, the non-aqueous electrolyte solution may contain a radicalscavenger, a surfactant, a flame retardant, and the like.

[Shape and Configuration of Battery]

The lithium ion secondary battery according to the present embodiment,the lithium ion secondary battery including the positive electrode, thenegative electrode, the separator, and the non-aqueous electrolytesolution described above can have various shapes such as a cylindricalshape and a stacked shape.

Whichever the lithium ion secondary battery has, the positive electrodeand the negative electrode are stacked with the separator interposedtherebetween to form an electrode body, and the electrode body isimpregnated with the non-aqueous electrolyte solution. The positiveelectrode collector is connected with a positive electrode terminalleading to the outside, and the negative electrode collector isconnected with a negative electrode terminal leading to the outside viaa current collecting lead or the like.

The lithium ion secondary battery having the above-mentionedconfiguration is enclosed in a battery case and the battery can becompleted.

EXAMPLES

Hereinafter, the present invention will be described in more detail byexamples and comparative examples, but the present invention is notlimited to the examples.

Example 1

[Metal Composite Hydroxide]

a) Manufacturing of Metal Composite Hydroxide Powder

[Preparing Process (a) of Metal Composite Hydroxide]

First, nickel sulfate hexahydrate, cobalt sulfate heptahydrate, andmanganese sulfate monohydrate were dissolved in water so that the molarratio of nickel, manganese, and cobalt was Ni:Mn:Co=35:30:35, and theconcentration of nickel, manganese, and cobalt was 2 [mol/L] to preparea raw material solution. In a reaction tank having a volume of 6 [L] upto overflow, 900 [ml] of water was put, the temperature in the reactiontank was raised to 40[° C.] using a water bath, and the inside of thereaction tank was adjusted to the atmosphere (oxygen concentration: 21[%by volume]).

Next, the raw material solution, ammonia water of 25[% by mass], andsodium hydroxide solution of 25[% by mass] were continuously suppliedwhile the water in the reaction tank was stirred to form a reactionsolution. At this time, the sodium hydroxide solution was supplied sothat the pH of the reaction solution was 11.7 at a standard liquidtemperature of 25[° C.], and the ammonia water was supplied so that theammonium ion concentration was maintained at 10.0 [g/L], so that thereaction solution was prepared.

In the state, crystallization treatment was performed for 0.5 hour, thenthe supply of the raw material solution, the ammonia water, and thesodium hydroxide solution was temporarily stopped, a nitrogen gas wasintroduced at a flow rate of 5 [L/min] and replaced the atmosphere untilthe oxygen concentration inside the reaction tank was 0.2[% by volume]or less, the liquid supply was restarted after a non-oxidizingatmosphere having an oxygen concentration of 0.2[% by volume] or lesswas obtained, and the crystallization treatment was continued. Then, theliquid supply was stopped again, the inside of the reaction tank wasreturned to the atmosphere, the liquid supply was restarted, and thecrystallization treatment was performed. The crystallization treatmentwas continued for a total of 4 hours while the reaction tank atmospherewas appropriately changed to the non-oxidizing atmosphere having anoxygen concentration of 0.2[% by volume] or less and the atmosphere.

Then, the slurry after the crystallization treatment was subjected tosolid-liquid separation to obtain a nickel-manganese-cobalt compositehydroxide Ni_(0.35)Mn_(0.30)Co_(0.35)(OH)₂ having a porous structure.

The pH and the ammonium ion concentration of the reaction solution weremeasured using Orion-Star-A214 (manufactured by Thermo Fisher ScientificK. K.) that is a pH/ammonia measurement kit (combined pH meter andammonium ion meter) previously placed in the reaction tank.

b) Washing of Metal Composite Hydroxide Powder

The metal composite hydroxide powder was slurried again withion-exchanged water so that the slurry concentration was 100 [g/L], asodium hydroxide solution was added, and the mixture was stirred for 30minutes to wash the metal composite hydroxide “with an alkali”. Theslurry washed with an alkali using the sodium hydroxide solution wassubjected to solid-liquid separation using a suction filter or the likeand then washed “with water” using pure water to perform the “filtrationand washing process (A)”, and the obtained washed residual material wasdried at 120[° C.] for 24 [hours] using an air dryer to obtain a drypowder of the metal composite hydroxide.

c) Evaluation of Metal Composite Hydroxide Powder

The composition of the metal composite hydroxide powder was measuredusing a simultaneous ICP optical emission spectrometer, ICPE-9000(manufactured by SHIMADZU CORPORATION), and as a result, it wasconfirmed that the composition was represented by a general formula:Ni_(0.35)Mn_(0.30)Co_(0.35)O.

[Fine Powder Lithium Compound]

A lithium compound powder as a lithium raw material is pulverized to apredetermined size in the pulverizing process (p). Specifically, lithiumcarbonate having a maximum particle size of 100 [μm] or more waspulverized using a jet mill (manufactured by, for example, SEISHINENTERPRISE Co., Ltd.) so that the maximum particle size was 10.0 [μm] orless and the average particle size was 5.0 [μm] or less to prepare apredetermined fine powder lithium compound. For the measurement of theparticle size distribution, a laser diffraction/scattering type particlesize distribution measuring device, Microtrac MT3300EX2 (manufactured byMicrotracBEL Corp.) was used.

The measurement results of the particle size distribution are shown inTable 1.

[Lithium Mixture]

a) Preparation of Lithium Mixture by Mixing Process (C)

The fine powder lithium compound was weighed to have a ratio to themetal composite hydroxide powder of Li/Me=1.02 and they were mixed toobtain a lithium mixture. For the mixing, a shaker mixer,TURBULA-TypeT2C (manufactured by Willy A. Bachofen AG (WAB)) was used.

b) Calcination and Firing of Lithium Mixture by Firing Process (D)

The lithium mixture was calcined in the air stream at 760[° C.] for 4hours, then fired at 900[° C.] for 10 hours, and cooled to roomtemperature to obtain lithium-metal composite oxide particles. Since thesecondary particles included in the lithium-metal composite oxide afterthe cooling were aggregated or slightly sintered, the secondaryparticles were subjected to deagglomeration and crushing to obtain apositive electrode active material.

[Positive Electrode Active Material]

Various characteristics of the manufactured positive electrode activematerial were evaluated by the method described below. The evaluationresults are shown in Table 1.

Slurry pH

For the measurement of the slurry pH, a pH/ion meter, HM-42X(manufactured by DKK-TOA CORPORATION) was used. For the calibration ofthe electrode, a phthalate pH standard solution (type 2: 4.01), aneutral phosphate pH standard solution (type 2: 6.86), a borate pHstandard solution (type 2: 9.18), and a carbonate pH standard solution(type 2: 10.01) that were standard buffer solutions for pH measurementmanufactured by Wako Pure Chemical Industries, Ltd. were used.

Soluble Lithium Content Rate

For the measurement of the soluble lithium content rate, a simultaneousICP optical emission spectrometer, ICPE-9000 (manufactured by SHIMADZUCORPORATION) was used.

Specific Surface Area

The specific surface was measured using a BET specific surface areameasuring device of Macsorb 1200 series (manufactured by Mountech Co.,Ltd.) employing a fluid type nitrogen gas adsorption method, andcalculated by the BET equation.

Porosity

For the cutting of the particles of the lithium-metal composite oxide, across-section polisher IB-19530CP (manufactured by JEOL Ltd.) that is across-section sample preparation device was used, and for theobservation of the cross section, a Schottky field emission scanningelectron microscope SEM-EDS, JSM-7001F (manufactured by JEOL Ltd.) wasused. Furthermore, by an image analysis and measurement software,WinRoof6.1.1 (manufactured by Mitani Corporation), the void in theparticle cross section was measured as a black part and the denseportion of the particle was measured as a white part, and an area ratioof the black part/(the black part+the white part) was calculated for any20 or more of the particles to determine the porosity.

Particle Strength

The particle strength was determined by applying a load to one NMCparticle with an indenter using a micro-strength evaluation testerMCT-500 (manufactured by SHIMADZU CORPORATION) and calculating theparticle strength when the particle was broken. Specifically, the NMCparticle was held stationary on a silicon plate, the position was finelyadjusted in accordance with the center of the indenter, and the indenterwas brought into contact with the NMC particle so that a large load wasnot applied to the NMC particle to perform the measurement. Themeasurement conditions were set so that the test force was 150 mN andthe load rate was 2.0 mN/sec, and the average value of 10 particles wasdetermined.

[Positive Electrode]

For the preparation of a positive electrode, the above-mentionedlithium-metal composite oxide as a positive electrode active material,acetylene black as a conductive material, and PVDF as a binding agentwere mixed so that the mass ratio was 85:10:5, then dispersed in asolvent (NMP), and formed into a paste. The positive electrode mixturepaste was applied to an aluminum foil (positive electrode collector)having a thickness of 20 [μm] using an applicator so that the mass perunit area of the positive electrode mixture paste was 7 [mg/cm²]. Then,the resulting product was dried at 120[° C.] for 30 minutes using anair-blow dryer, and then rolled with a load of a linear pressure of 180[kg/cm] by a roll press to obtain a positive electrode sheet.

The positive electrode sheet was punched into a 3×5 [cm] rectangle witha 10 [mm] wide strip (terminal) protruding from one corner of the sheet,the positive electrode active material layer was removed from the strip,and the aluminum foil was exposed to form a terminal portion, so that apositive electrode sheet with a terminal was obtained.

For the measurement of the viscosity of the positive electrode mixturepaste for viscosity confirmation prepared under the above-mentionedconditions, a vibrating viscometer, VISCOMATE VM-100A (manufactured bySEKONIC CORPORATION) was used, and a standard solution manufactured byNIPPON GREASE Co., Ltd. was used as the standard solution forcalibration of a viscometer that is specified in JIS-Z-8809 (JS-200,JS-2000).

[Negative Electrode]

For the preparation of a negative electrode, natural graphite powder(manufactured by Mitsubishi Chemical Corporation) as a negativeelectrode active material and PVDF (binder) as a binding agent weremixed so that the mass ratio was 90:10, then dispersed in a solvent(NMP), and formed into a paste. The paste was applied to a coppercurrent collector (negative electrode collector) having a thickness of15 [μm] using an applicator so that the paste had the thickness of 3.1[mg/cm²]. Then, the resulting product was dried at 120[° C.] for 30minutes using an air-blow dryer. Furthermore, the dried electrode wasrolled under a linear pressure of 390 [kg/cm] using a roll press toobtain a negative electrode sheet.

The prepared negative electrode sheet was cut into a 3.2×5.2 [cm]rectangle with a 10 [mm] wide strip (terminal) protruding from onecorner of the sheet, the negative electrode active material layer wasremoved from the strip, and the copper foil was exposed to form aterminal portion, so that a negative electrode sheet with a terminal wasobtained.

[Separator]

As a separator, a polypropylene microporous film separator having athickness of 20 [μm] generally used in a lithium ion secondary batterywas cut into 5.8×3.4 [cm] and used.

[Electrolyte Solution]

For the preparation of an electrolyte solution, ethylene carbonate (EC)and ethyl methyl carbonate (EMC) were mixed at a volume ratio ofEC/EMC=3:7 to prepare a mixed solution containing lithiumhexafluorophosphate (LiPF₆) as a supporting electrolyte at a content of1 [mol/L], and the mixed solution was used as an electrolyte solution.

[Assembly]

Above-mentioned materials were dried under reduced pressure at 80[° C.]for 8 hours, then brought into a dry room in which the dew point wasless than −60[° C.], and assembled into a single-layer laminate cellbattery having an exterior size of 80×60 [mm] shown in FIG. 4 . FIG. 4shows a single-layer laminate cell battery C used in the present examplein which a positive electrode sheet is represented by 1, a negativeelectrode sheet is represented by 2, a separator is represented by 3, analuminum laminate sheet is represented by 4, and a heat-sealed portionis represented by HS.

[Conditioning Process]

The battery was held in a thermostat controlled at 25[° C.] with a loadof 0.4 [kgf/cm²] applied to the electrode portion, kept for 12 hours,and then charged to 4.2 [V] at a rate of 0.2 [C] (a current value forfull charge in 5 hours) and discharged to 3.0 [V] at a rate of 0.2 [C]using charge and discharge test device HJ1001SD8 (manufactured by HOKUTODENKO CORPORATION) with a rest time of 10 minutes after the charge anddischarge.

[Lithium Ion Secondary Battery]

—Evaluation of Low-Temperature Output Characteristic—

Using the laminate cell for evaluation shown in FIG. 4 , the internalresistance of the battery at a low temperature (—20[° C.])ΔV_(−20[° C.]) was measured by a current rest method to evaluate thelow-temperature output characteristic. The method for evaluation isshown below.

The laminate cell for evaluation is prepared as shown below.

The positive electrode active material, the conductive material(acetylene black), and the binding agent (PVDF) are mixed so that themass ratio is 85:10:5, then the solvent (NMP) was added to form a paste,the paste was applied to the aluminum current collecting foil (thickness0.02 [mm]) excluding the conductive portion connected to the outside,and the resulting product was dried to prepare a positive electrodesheet 1 in which a positive electrode active material layer is formedhaving a weight per unit area of the positive electrode active materialof 7 [mg/cm²].

Furthermore, natural graphite powder as the negative electrode activematerial and the binding agent (PVDF) are mixed so that the mass ratiois 90:10, then dispersed in the solvent (NMP) to form a paste, and thepaste was applied to the copper current collecting foil (thickness 0.02[mm]) to prepare a negative electrode sheet 2 in which a negativeelectrode active material layer is formed having a weight per unit areaof the negative electrode active material of 5 [mg/cm²].

Between the prepared positive electrode sheet 1 and the negativeelectrode sheet 2, a separator 3 including the polypropylene microporousfilm (thickness 20.7 [μm], porosity density 43.9[%]) was interposed toform a laminate sheet, the laminate sheet was sandwiched between twoaluminum laminate sheets 4 (thickness 0.55 [mm]), and the three sides ofthe aluminum laminate sheets 4 are heat-sealed to form a heat-sealedportion HS, so that the aluminum laminate sheets 4 were sealed andassembled into a laminate cell having a configuration as shown in FIG. 4.

Then, after injecting 260 [μl] of an electrolyte solution manufacturedby Ube Industries, Ltd. in which lithium hexafluorophosphate (LiPF₆) wasdissolved at a content of 1 [mol/L] in a mixed solvent of ethylenecarbonate, ethyl methyl carbonate, and dimethyl carbonate (volume ratio3:3:4), the remaining one side was heat-sealed to prepare an assembledlaminate cell shown in FIG. 4 .

The prepared laminate cell was charged to 4.2 [V] at a temperature of−20[° C.] and then discharged to 2.5 [V] at 0.2 [C], the voltage wasrelaxed in an open circuit for 600 seconds, and the voltage changebefore and after relaxing the voltage (ΔV_(−20[° C.])) was calculated.When the current is constant during the discharge, the obtained voltagechange (ΔV_(−20[° C.])) can be regarded as the resistance change. Thatis, the smaller ΔV_(−20[° C.]) is, the lower the “battery resistance”can be regarded as, so that the value of ΔV_(−20[° C.]) was used as anindex of the DC resistance under a low temperature condition to evaluatethe “low-temperature output characteristic” of the secondary battery inthe present example.

The evaluation results are shown in Table 1.

Example 2

A positive electrode active material was obtained in the same manner asin Example 1 except that the lithium carbonate was pulverized using ajet mill until the lithium carbonate had the particle size distributionof a maximum particle size of 8.0 [μm] or less and an average particlesize of 4.0 [μm] or less to perform evaluation.

The evaluation results are shown in Table 1.

Example 3

A positive electrode active material was obtained in the same manner asin Example 1 except that the lithium carbonate was pulverized using ajet mill until the lithium carbonate had the particle size distributionof a maximum particle size of 4.1 [μm] or less and an average particlesize of 2.5 [μm] or less to perform evaluation.

The evaluation results are shown in Table 1.

Example 4

A positive electrode active material was obtained in the same manner asin Example 1 except that the lithium carbonate was pulverized using ajet mill until the lithium carbonate had the particle size distributionof a maximum particle size of 4.0 [μm] or less and an average particlesize of 2.0 [μm] or less to perform evaluation.

The evaluation results are shown in Table 1.

Comparative Example 1

A positive electrode active material was obtained in the same manner asin Example 1 except that the lithium carbonate was not pulverized andhad the particle size distribution of a maximum particle size of 110[μm] and an average particle size of 53 [μm] to perform evaluation.

The evaluation results are shown in Table 1.

Comparative Example 2

A positive electrode active material was obtained in the same manner asin Example 1 except that the lithium carbonate was not pulverized andhad the particle size distribution of a maximum particle size of 120[μm] and an average particle size of 65 [μm] to perform evaluation.

The evaluation results are shown in Table 1.

TABLE 1 Lithium ion secondary Lithium compound (lithium carbonate)Positive electrode active material battery Pulverizing Soluble SpecificCurrent Maximum Average Maximum Average Positive electrode lithiumsurface Particle rest particle particle particle particle mixture pasteSlurry [% by area Porosity strength method size size size size ViscositypH weight] [m²/g] [%] (MPa) ΔV_(−20 [° C.]) [μM] [μM] [μM] [μM] [mPa ·s] Gelation Example 1 11.4 0.45 3.02 53 158 0.49 110 53 9.8 4.7 4900 Notcaused Example 2 11.4 0.44 3.35 62 135 0.48 110 53 7.8 3.9 4500 Notcaused Example 3 11.2 0.20 3.70 71 124 0.45 110 53 4.1 2.3 3300 Notcaused Example 4 11.0 0.04 3.93 78 106 0.42 110 53 3.6 1.5 1800 Notcaused Comparative 11.8 0.54 2.91 34 — 0.54 110 53 Not Not 7200 CausedExample 1 pulverized pulverized Comparative 12.0 0.63 2.75 26 — 0.58 12065 Not Not 8500 Caused Example 2 pulverized pulverized

[Comprehensive Evaluation]

The positive electrode active materials in Examples 1 to 4 had theeffect of improving the reactivity in the calcination and main firingprocess by use of the fine powder lithium compound prepared bypulverizing the lithium compound (lithium carbonate) as a lithium rawmaterial having a maximum particle size of 100 [μm] or more, and theslurry pH, the soluble lithium content, the specific surface area, andthe porosity were all within the preferable ranges. Furthermore,gelation was not caused during the preparation of the positive electrodemixture paste, and the positive electrode mixture paste had a viscosityof 5,000 [mPa·s] or less at a ratio of the solid component [g]/thesolvent [g]=1.875 at 20[° C.].

In a lithium ion secondary battery incorporating the positive electrodeactive material, the ΔV_(−20[° C.]) determined by a current rest methodwas low at −20[° C.], so that it was confirmed that the lithium ionsecondary battery having an excellent characteristic was obtained by useof the above-mentioned materials.

In addition, it is considered that the specific surface area wasincreased because during the reaction between the lithium compound(lithium carbonate) and the metal composite hydroxide, the fine powderlithium compound was interposed in the grain boundary portion of themetal composite hydroxide and the grain growth of the positive electrodeactive material was hindered. It is presumed that the contact area ofthe particle surface of the positive electrode active material wasincreased to make lithium extraction/insertion easy, and thelow-temperature output characteristic was improved.

On the other hand, in the positive electrode active materials inComparative Examples 1 and 2, gelation was slightly caused during thepreparation of the positive electrode mixture paste, and the viscosityof the positive electrode mixture paste and the ΔV determined by acurrent rest method at −20[° C.] in a lithium ion secondary batteryincorporating the positive electrode active material wereunsatisfactory. It is considered that the reason is that the unreactedexcessive lithium was increased and the crystallinity of the positiveelectrode active material was deteriorated because of the reducedreactivity due to the lithium compound (lithium carbonate) calcinatedand mainly fired without pulverizing.

From the above results, the non-aqueous electrolyte secondary batteryusing the positive electrode active material of the present example hasan excellent low-temperature output characteristic and the like, so thatit is possible to realize a non-aqueous secondary battery from whichhigh output can be extracted regardless of use environment.

The non-aqueous electrolyte secondary battery according to the presentinvention is suitable as a power source for devices expected to be usedin various environments such as electric cars and hybrid vehicles, andthus has a very large industrial applicability.

REFERENCE SIGNS LIST

-   1 Positive electrode sheet-   2 Negative electrode sheet-   3 Separator-   4 Aluminum laminate sheet-   11 Composite hydroxide particles-   12 Primary particles-   13 Secondary particle-   14 Void-   C Single-layer laminate cell battery-   d Particle size-   HS Heat-sealed portion

The invention claimed is:
 1. A positive electrode active material fornon-aqueous electrolyte secondary batteries, the positive electrodeactive material comprising: a lithium-metal composite oxide powderincluding a secondary particle configured by aggregating primaryparticles containing lithium, nickel, manganese, and cobalt, or alithium-metal composite oxide powder including both the primaryparticles and the secondary particle, wherein the secondary particle hasa porous internal structure, a mixed slurry being a mixture of water andthe lithium-metal composite oxide powder as a slurry solid bodycomponent has a pH of 11.5 or less at a time when the mixed slurrycontains the lithium-metal composite oxide powder at a slurryconcentration of 50 [g/L], the lithium-metal composite oxide powdercontains soluble lithium at a content rate of 0.5[% by mass] or less,the lithium-metal composite oxide powder has a specific surface area of3.0 to 4.0 [m²/g], and the secondary particle has a porosity of morethan 50 to 80[%].
 2. The positive electrode active material fornon-aqueous electrolyte secondary batteries, according to claim 1,wherein the lithium-metal composite oxide powder is represented by ageneral formula: Li_(a)(Ni_(1-w-x)Mn_(w)Co_(x))_(1-y)M_(y)O₂:(0.98≤a≤1.20, 0.01≤w≤0.50, 0.01≤x≤0.50, 0.01≤y≤0.10, where M is one ormore of Mg, Al, Ti, Fe, Cu, Si, Zn, Mo).
 3. The positive electrodeactive material for non-aqueous electrolyte secondary batteries,according to claim 1, wherein the lithium-metal composite oxide powderhas a particle strength of 100 to 160 MPa.
 4. A non-aqueous electrolytesecondary battery comprising a positive electrode including the positiveelectrode active material for non-aqueous electrolyte secondarybatteries according to claim 1, wherein ΔV_(−20[° C.]) determined by acurrent rest method is 0.50 [V] or less at −20[° C].
 5. A positiveelectrode mixture paste for non-aqueous electrolyte secondary batteries,the positive electrode mixture paste comprising: a solid component; anda solvent, wherein the solid component contains the positive electrodeactive material for non-aqueous electrolyte secondary batteriesaccording to claim 1, and the positive electrode mixture paste has aviscosity of 5,000 [mPa·s] or less at 20[° C.] at a time when the solidcomponent and the solvent have a mass ratio of the solid component[g]/the solvent [g] =1.875.
 6. A method for manufacturing a positiveelectrode active material for non-aqueous electrolyte secondarybatteries, the method comprising: a filtration and washing process (A)of washing a metal composite hydroxide with water, or with an alkali andthen with water, and collecting a residual material of the metalcomposite hydroxide by a solid-liquid separation; a drying process (B)of obtaining a dried material of the metal composite hydroxide by dryingthe residual material; a mixing process (C) of forming a mixture of thedried material and a fine powder lithium compound having a maximumparticle size of 10 [μm] or less; and a firing process (D) of forming apositive electrode active material for non-aqueous electrolyte secondarybatteries, the positive electrode active material including alithium-metal composite oxide as a fired body by firing the mixture,wherein a lithium-metal composite oxide powder is manufactured with themetal composite hydroxide containing nickel, manganese, and cobalt andthe fine powder lithium compound having a maximum particle size of 10[μm] or less as raw materials using a manufacturing process includingthe processes (A) to (D) in order described above, the lithium-metalcomposite oxide powder includes a secondary particle configured byaggregating primary particles containing lithium, nickel, manganese, andcobalt or includes both the primary particles and the secondaryparticle, the secondary particle has a porous internal structure, thelithium-metal composite oxide powder has a porosity of more than 50 to80[%], a slurry has a pH of 11.5 or less at a time when a slurryconcentration is 50 [g/L], the lithium-metal composite oxide powdercontains 0.5[% by mass] of soluble lithium, and the lithium-metalcomposite oxide powder has a specific surface area of 3.0 to 4.0 [m²/g].7. The method for manufacturing a positive electrode active material fornon-aqueous electrolyte secondary batteries, according to claim 6,wherein the metal composite hydroxide is produced by a preparing process(a) described below, and the metal composite hydroxide has a coarsedensity of more than 50 to 80[%]: a preparing process (a) for producinga metal composite hydroxide, the preparing process of stirring waterhaving a water surface in an oxidizing atmosphere and having amaintained temperature of 40 to 60[° C.]; forming a reaction solution byadding a nickel-manganese-cobalt mixed solution, ammonia water, and analkaline aqueous solution to the water while the water is stirred;performing a crystallization treatment in a state where the reactionsolution has a maintained pH of 11.0 to 12.5; repeating acrystallization treatment in the reaction solution having a liquidsurface in an inert atmosphere or in a non-oxidizing atmosphere having acontrolled oxygen concentration of 0.2[% by volume] or less, and acrystallization treatment in the reaction solution having a liquidsurface in an oxidizing atmosphere having an oxygen concentration ofmore than 21[% by volume]; and crystallizing a metal composite hydroxidehaving a controlled coarse density of more than 50 to 80[%].
 8. Themethod for manufacturing a positive electrode active material fornon-aqueous electrolyte secondary batteries, according to claim 6,wherein a lithium raw material of the fine powder lithium compound, thelithium raw material before pulverized is a lithium compound powderhaving a maximum particle size of 100 [μm] or more and an averageparticle size of 50 [μm] or more.
 9. The method for manufacturing apositive electrode active material for non-aqueous electrolyte secondarybatteries, according to claim 8, wherein the lithium raw material islithium carbonate, lithium hydroxide, or a mixture of the lithiumcarbonate and the lithium hydroxide.
 10. The method for manufacturing apositive electrode active material for non-aqueous electrolyte secondarybatteries, according to claim 6, wherein the fine powder lithiumcompound has a maximum particle size of 10 [μm] or less and an averageparticle size of 5.0 [μm] or less, and the fine powder lithium compoundis formed using a pulverizing process (p) described below: a pulverizingprocess (p) of producing a fine powder lithium compound having a maximumparticle size of 10 [μm] or less and an average particle size of 5.0[μm] or less by pulverizing a lithium compound powder being a lithiumraw material having a maximum particle size of 100 [μm] or more and anaverage particle size of 50 [μm] or more.
 11. The method formanufacturing a positive electrode active material for non-aqueouselectrolyte secondary batteries, according to claim 6, wherein thelithium-metal composite oxide powder is represented by a generalformula: Li_(a)(Ni_(1-w-x)Mn_(w)Co_(x))_(1-y)M_(y)O₂: (0.98≤a≤1.20,0.01≤w≤0.50, 0.01≤x≤0.50, 0.01≤y≤0.10, where M is one or more of Mg, Al,Ti, Fe, Cu, Si, Zn, Mo).